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Presented by:MarzenaMikos‐SzymańskaFertilizer Department,INSPuławy,PolandE‐mail:marzena.mikos‐[email protected]

SebastianSchab,PiotrRusek,KrzysztofBorowik

Preliminary study of a method for obtaining brown coal and biochar based granular

compound fertilizer

6th International Conference on Sustainable Solid Waste

Management

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NEW CHEMICAL SYNTHESES INSTITUTE

13-16 June 2018, Naxos Island, Greece

INTRODUCTION

Brown coal (BC) that is characterized by very low heating value can be used as a component of organo-mineral fertilizers

BC contains organic matter in a complex, porous, three-dimensional network, which varies depending on deposit location

The porous structure and functional groups of BC are important for betternutrient retention and microbial activity in soil

BC is an alternative material with properties that make it appealing for use as a N fertilizer carrier

Brown coal – urea blended fertilizers show potential for more efficient use of N in the long term and has environmental benefits in retaining more N in the soil (Rose et al., 2016)

Improving nutrient use efficiency (NUE) and reversing the loss of soil organic matter are major challenges facing farmers worldwide

HUMIC ACIDS

Fig. 1. Hypothetical primary structure of a leonardite humic acid

Source: Erro et al., Chem. Biol. Technol. Agric. (2016) 3:18

Humic acids are very important components of brown coal and can account 10-80% of its organic matter (Allard, 2006)Humic acids contain many

functional chemical groups that help to physically modify and improve the chemical properties of the soil and biologically stimulate plant growthHumic acid products mainly as

plant growth enhancers and as ingredients in fertilizer products are widely distributed throughout the world

BIOCHAR

• Biochar can contain certain amounts of extractable humic-like and fulvic-like substances (Lin et al., 2012).

• A number of studies show that biochars can reduce nitrate and ammonium leaching from applied nitrogen fertilizers, but the effectiveness depends on the chemical characteristics of biochars and their rate of application (Manikandan and Subramanian, 2013; Rose et al., 2016; Saha et al., 2017)

PURPOSE

The aim of the research was:to develop a method for the production of a brown-coal based

compound granular fertilizer with improved efficiency, easily available humic acids, and urea in the form of an adduct: CaSO4·4CO(NH2)2

to use biochar for coating the compound granular fertilizer to evaluate the effect of brown coal based fertilizer and biochar

coated fertilizer on wheat growth

The quality of obtained fertilizer products and the possibility of using brown coal and biochar as components of mineralUSP fertilizer was evaluated.

RAW MATERIALS

• Phosphorite (Djebel Onk, Algeria) was bought from the Chemical Plant "Siarkopol" TARNOBRZEG Sp. z o.o. (Poland)

• Granular urea (46% N) - Grupa Azoty Puławy SA (GAP SA)(Poland)• Technical sulfuric acid (conc. 95%) - GAP SA (Poland)• Gaseous ammonia (NH3 – min 99.8 % wt.) – GAP SA (Poland)• Caustic magnesite - MAGNEZYTY "GROCHÓW" S.A. (Inc.) company (Poland)• Dolomite - Dolomite Mining Company, Górnicze Zakłady Dolomitowe SA,

Siewierz Mine (Poland)• Run-of-mine brown coal from Brown Coal Mine “Sieniawa” (Poland)• Biochar 1 - plant material after extraction, Pyreg (Germany) • Biochar 2 - energy-crop willow, University of Limerick (Ireland) • Biochar 3 - wood chips, Fluid SA (Poland) • USP fertilizer* (21% N, 10% P2O5, 15.9% CaO, and 7.9% S) – INS (Poland)

* EP Application no. EP 2 774 907 (Biskupski et al., 2014)

PHYSICO-CHEMICAL PROPERTIES

Parametr Unit Brown coal

Biochar 1 Biochar 2 Biochar 3

pHH2O, AR - 4.3 10.3 9.6 7.4Electrical conductivity (EC), AR (µS·cm-1) 1362 2190 353 483

Loss on ignition (LOI), 550°C; 3.5h, DM (%) 84.45 87.28 94.89 95.99Water content, 105°C, 4h, AR (%) 47.70 45.64 5.98 3.09

Pb, DM1 (mg·kg-1) <4.0 <4.0 <4.0 -Cd, DM1 (mg·kg-1) <1.0 1.58 <1.0 -

Total humic acids, DM2 (%) 51.02 6.50 6.89 -Free humic acids, DM2 (%) 49.20 4.49 3.44 -

C, DM3 (%) 53.46 63.5*) 85.80 84.44H, DM3 (%) 4.42 0.95*) 1.36 1.99N, DM3 (%) 0.76 1.80*) 0.74 0.57

Molar ratio H/C - 0.99 0.18*) 0.19 0.28Footnotes: 1determined by ICP-OES; 2humic acids determined according to BS ISO 5073:2013; 3

determined by combustion using Perkin Elmer 2400 series CHN analyzer; *) results from biochar certificate, DM – dry matter, AR – as received, - not determined

LAB GRANULATION

Binding agent preparation

Bulkmaterials

mixingPan

granulation Drying

457 g of urea (46% N) 217 g of technicalsulfuric acid (95%) 28.2 g of water

1890 g of wet coal336 g of phosphorite

Time of granulation -less than 15 minutesPan granulator diameter– 400 mm

90°C, 1h

Cube mixer (ERWEKA GmbH, Germany)

Pan granulator(ERWEKA GmbH, Germany

Lab dryerHotplate

LAB GRANULATION RESULTS

Parameter ResultMoisture content (105°C, 4h) (%) 30.2pH of air-dried sample 2.4pH of dried sample at 105°C 3.7

Low particle hardnessFor the average size of

granules (4.26 mm), the average particle hardness was 2.3 NGranules were classified as

“soft” because they very easy crushed between the thumb and forefinger (UNIDO and IFDC, 1998)

The research on the binder agentselection and raw material ratiosshould be studied in order to increase the particle hardness of the fertilizer product.

GRANULATION IN LARGE SCALE

Urea-sulfuric acid solutionpreparation – a reactor with a heating coat (t=90°C)

Preliminary mixing of bulkmaterials in a intensive granulator (20 L), turbine speed – 250 rpm,

vessel speed – 120 rpm

Granulation (time =20 min)

Drying

RAW MATERIAL CONSUMPTION

No. of trial

Raw material consumption (% wt.)brown coal

(BC), DM

urea phosphorite H2SO4,100%

dolomite(D)

caustic magnesite

(M)

H2O NH3(g)

1 50.0 22.8 16.8 10.4 - - 2.7 -2 45.5 20.8 15.3 9.4 9.0 - 2.5 -3 50.0 22.8 16.8 10.4 - - 2.7 +4 47.5 21.7 16.0 9.9 - 5.0 2.6 -

CHEMICAL PROPERTIES OF THE BROWN COAL BASED FERTILIZERS

Parameter Unit Trial 1 Trial 2 Trial 3 Trial 4BC+USP BC+USP+D BC+USP+NH3(g) BC+USP+M

Moisture content (105°C; 3h) % 29.0 25.7 - -Moisture content (90°C; 1h) % - - 9.3 8.3

pH - 2.6 3.3 5.4 6.2Ntot. % 9.85 9.83 9.58 8.26

P2O5tot. % 4.39 3.76 3.85 3.67NAC+H2O soluble P2O5 % 3.72 3.21 3.03 2.86

H2O soluble P2O5 % 2.60 2.33 1.77 0.69Mg % - 1.38 - 1.88Ca % - 5.90 - 4.30

Loss on ignition105°C % 31.32 28.70 31.50 30.20400°C % 72.54 64.55 74.53 70.67

1000°C % 81.91 73.98 82.61 77.64Footnotes: NAC+H2O - neutral ammonium citrate and water soluble

Method of nutrient determination according to the methods dedicated for the fertilizer quality analysis (EC Regulation No 2003/2003)

PARTICLE HARDNESS (N)

Parameter Unit Trial 1 Trial 2 Trial 3 Trial 4Average granule size mm 4.04 3.94 4.04 3.90Average particle hardness N 23.30 18.18 20.05 15.80Percentage of weak granules % 10 20 25 30Average particle hardness afterexcluding weak granules

N 24.89 21.12 23.38 19.62

Trial 1. BC+USP Trial 2. BC+USP+D Trial 3. BC+USP+NH3 Trial 4. BC+USP+M

PARTICLE SIZE DISTRIBUTION

Trial 1

Trial 2

Trial 3

Trial 40

10

20

30

40

50

2.0

2.5

3.15

4.0

5.0

Mas

s fra

ctio

n (%

)

Sieve size (mm)

A vibratory sieve shaker (Retch AS 200, Germany

Fig. 2. Sieve analysis of brown coal based fertilizer

HYGROSCOPICITY

Fig. 3. Weight changes (%) of browncoal under different relativehumidity

Fig. 4. Weight changes (%) of biochar 3 under different relativehumidity

Brown coal sample undergoes naturaldrying process.After 7 days, BC contained 10-17% of moisture.

Biochar sample is hygroscopic.After 7 days in discicator, B3 sample storedat humidity of 56-74% , absorbs about 5% wt. of water.

HYGROSCOPICITY

Fig. 5. Weight changes (%) of BC+USP sample under differentrelative humidity

Fig. 6. Weight changes (%) of BC+USP+NH3 under differentrelative humidity

The weight losses of brown coal based fertilizers was about 15-19% wt. because of water desorption to the environment

COATING OF USP FERTILIZER GRANULES

A pan granulator (ERWEKA GmbH, Germany)While USP fertilizer granules were rotating in the pan granulator, the biochar was added and water was sprayed using a hand sprayer (KwazarCorporation Sp. z o.o., Poland)The samples were called: B1CF - biochar from a plant material after

extraction, B2CF - biochar from energy-crop willow, B3CF - biochar from wood chips.

Biochar constituted 10% wt. of the total granules mass.

BIOCHAR COATED FERTILIZER

Parameter Unit B1CF B2CF B3CF FAverage granule size mm 4.46 4.16 4.28 4.46Average particle hardness N 41.65 45.20 49.50 61.90Abrasion resistance % 2.5 6.1 7.8 0.7

B1CF – biochar 1 coatedUSP

B2CF – biochar 2coated USP

B3CF – biochar 1coated USP

F – USP fertilizer

GREENHOUSE EXPERIMENT

0

10

20

30

40

50

60

Plan

t hei

ght(

cm)

T. aestivum T. durum

Fig. 7. Plant height (cm) at the booting stage of wheat development.

Each treatment received the same dose of NPK before sowing (2.4 g N, 1.3 g P2O5, 2 g K2O per a pot).

CONCLUSIONS

Brown coal and biochar can be used as raw materials for fertilizer productionBrown coal contained about 50% of total humic acids

while biochar conatined nearly 6% of total humic-likesubstancesBrown coal based fertilizer produced in lab scale using a

pan granulator were classified as ’soft’ so the studies areneeded to choose a special binder and appropriate rawmaterial ratios to increase their particle hardnessBrown coal based fertilizer granules produced in small

scale using a rapid mixer granulator were characterizedby promising hardness and particle size distributionBiochar can be used for USP fertilizer coating but the

more studies are needed to choose the special bindingagent in order to reduce abrasion resistance of granules

Thank you!

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Fertilizer Research Centre, INS